CN115849762B - Anti-seepage and anti-corrosion marine concrete composite additive and preparation method thereof - Google Patents
Anti-seepage and anti-corrosion marine concrete composite additive and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
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- 230000000996 additive effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 17
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- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 73
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 44
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- 238000002156 mixing Methods 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 29
- -1 ester quaternary ammonium salt Chemical class 0.000 claims description 29
- 239000012752 auxiliary agent Substances 0.000 claims description 28
- 239000008236 heating water Substances 0.000 claims description 28
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 230000003014 reinforcing effect Effects 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 21
- 229920002873 Polyethylenimine Polymers 0.000 claims description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- 230000002265 prevention Effects 0.000 claims description 21
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 229920005646 polycarboxylate Polymers 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical group CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 9
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 9
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 9
- 229940043276 diisopropanolamine Drugs 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000013535 sea water Substances 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
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- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 7
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
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- 239000004568 cement Substances 0.000 description 1
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- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a marine concrete composite additive with impermeability and corrosion resistance and a preparation method thereof, belonging to the technical field of marine concrete additives. The invention adopts the water-soluble polyvinyl alcohol fiber to modify the polyester fiber, improves the cohesiveness of the modified reinforced polyester fiber and the concrete matrix, and reduces the generation of cracks. The composite nano silicon dioxide is added to enhance the compactness, improve the impermeability, and act together with the polyester fiber to improve the compactness and toughness of the concrete matrix, thereby effectively preventing Cl ‑ And the invasion of harmful substances, such as seawater and the like, can be prevented from being corroded by the harmful substances contained in the seawater, and the seawater and the harmful substances are matched with each other, so that the comprehensive performance, particularly the strength performance and the corrosion resistance performance, of the marine concrete are greatly improved. The admixture improves the impermeability, chloride ion and sulfate corrosion resistance of the marine concrete, improves the durability of the marine concrete and prolongs the service life of the marine concrete.
Description
Technical Field
The invention belongs to the technical field of marine concrete additives, and particularly relates to a marine concrete composite additive with impermeability and corrosion resistance and a preparation method thereof.
Background
The coastline of China is longer, and the ocean economy is a very important component of the national economy of China. However, the marine concrete structure is in a severe environment, and seawater has a strong corrosion effect on the reinforced concrete structure, so that the service life of the marine concrete structure is short, and the development of marine economy is greatly influenced. Numerous examples show that the failure of most marine concrete structures is not caused solely by load, but is mainly caused by Cl - Under severe marine environments rich in chloride ions, sulfate and other salts, salt ions continuously permeate into the concrete, so that passivation films of the steel bars are damaged, corrosion of the steel bars is caused, and the whole concrete structure is damaged. Factors influencing the service life of marine concrete mainly include the following: the compactness of concrete, chemical corrosion resistance, corrosion of steel bars and the like. Therefore, the method improves the compactness and the impermeability of the concrete, reduces shrinkage cracking, and is a key for improving the corrosion resistance of the concrete to seawater and other harmful media and improving the durability of the concrete structure.
The additive is a material with small mixing amount and great influence on the performance of concrete, and is one of the indispensable components for developing marine concrete. At present, the commonly used marine concrete additive has single performance, and although the strength performance of the marine concrete can be improved to a certain extent, the effect is limited.
Disclosure of Invention
The invention provides an anti-seepage and anti-erosion marine concrete composite additive which is suitable for seawater and other corrosive environments, on one hand, the compactness and anti-seepage performance of concrete can be effectively improved, chloride ions and sulfate erosion can be effectively reduced, and on the other hand, the strength of a concrete matrix can be improved, and the durability of marine concrete can be greatly improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the marine concrete composite additive with impermeability and corrosion resistance is prepared from the following raw materials in parts by weight: 10-15 parts of polycarboxylate water reducer, 0.2-2 parts of reinforcing component, 0.1-0.5 part of corrosion and rust prevention auxiliary agent, 2-5 parts of composite nano silicon dioxide, 10-15 parts of modified polyester fiber, 5-10 parts of alkali-free rapid hardening component, 0.1-0.5 part of air entraining agent and 25-35 parts of water.
Further, the reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1: 1-3.
Further, the corrosion inhibition and rust prevention auxiliary agent is dodecenyl succinic acid and hydroxyethylene diphosphonic acid according to the mass ratio of 1: 1-3.
Further, the preparation method of the composite nano silicon dioxide comprises the following steps: heating water to 40-50 ℃, dissolving sodium methacrylate in water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
Further, the purity of the hydrophilic nano silicon dioxide is more than 99.8%, the average particle diameter is 7-8nm, and the specific surface area is 380+/-30 m 2 /g。
Further, the mass ratio of the water to the methacrylic acid to the octylphenol polyoxyethylene ether to the polyethyleneimine to the sodium methallyl sulfonate to the hydrophilic nano silica is 20-30:3-5:5-10:3-5:3-5:100.
Further, the preparation method of the modified polyester fiber comprises the following steps: heating water to 85-90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 5-10:100:1-3:100.
Further, the alkali-free rapid hardening component comprises aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to the mass ratio of 20-25:2-4:2-4: 3-7.
A preparation method of a marine concrete composite additive with impermeability and corrosion resistance comprises the following steps:
A. preparing composite nano silicon dioxide: heating water to 40-50 ℃, dissolving sodium methacrylate in the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide;
B. preparing modified polyester fiber: heating water to 85-90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 5-10:100:1-3:100;
C. 10-15 parts of polycarboxylate water reducer, 0.2-2 parts of reinforcing component, 0.1-0.5 part of corrosion and rust prevention auxiliary agent, 2-5 parts of composite nano silicon dioxide, 10-15 parts of modified polyester fiber, 5-10 parts of alkali-free quick setting component, 0.1-0.5 part of air entraining agent and 25-35 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
The raw materials used in the present invention are commercially available.
The admixture of the invention accounts for 2 to 4 percent of the dosage of the concrete.
Advantageous effects
In the invention, the water-soluble polyvinyl alcohol fiber is adopted to modify and increase the polyester fiber, so that the modified and reinforced polyester fiber plays a role in bonding when the mixed concrete is dissolved, the bonding performance of the modified and reinforced polyester fiber and a concrete matrix is improved, the generation of cracks is reduced, and the anti-cracking strength is improved. Under the action of water, the composite nano silicon dioxide forms a layer of waterproof film which can fill capillary pores in cement mortar or concrete, strengthen the compactness, improve the impermeability, and improve the compactness and toughness of a concrete matrix by coaction with polyester fibers, thereby effectively preventing Cl - Invasion of harmful substances such as seawater and the like can be prevented, and erosion of the harmful substances contained in the seawater can be prevented; the two are matched with each other, so that the comprehensive performance, particularly the strength performance and the corrosion resistance performance of the marine concrete are greatly improved. Meanwhile, the invention also adds an air entraining agent and an alkali-free rapid hardening component, forms tiny bubbles in the early hydration process of the concrete, seals a plurality of capillary channels in the concrete structure, reduces the appearance defect of the concrete and improves the interface characteristic. The introduction of the corrosion inhibition and rust prevention auxiliary agent can reduce the concentration of the invasive sulfate ions, refine the pore diameter of capillary pores and effectively improve the sulfate erosion resistance of the concrete. In combination, the combined action of the raw materials obviously improves the impermeability, chloride ion and sulfate corrosion resistance of the marine concrete, enhances the corrosion resistance of the marine concrete, improves the durability of the marine concrete, and further improves the service life of the marine concrete.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The marine concrete composite additive with impermeability and corrosion resistance is prepared from the following raw materials in parts by weight: 10 parts of polycarboxylate water reducer, 0.2 part of reinforcing component, 0.1 part of corrosion inhibition and rust prevention auxiliary agent, 2 parts of composite nano silicon dioxide, 10 parts of modified polyester fiber, 5 parts of alkali-free rapid hardening component, 0.1 part of air entraining agent and 25 parts of water.
The reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1: 1.
The corrosion and rust inhibition auxiliary agent comprises the components of dodecenyl succinic acid and hydroxyethylidene diphosphonic acid according to the mass ratio of 1: 1.
The composite nano silicon dioxide is prepared by the following method: heating water to 40 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
The purity of the hydrophilic nano silicon dioxide is more than 99.8%, the average grain diameter is 7-8nm, and the specific surface area is 380+/-30 m 2 /g。
The mass ratio of the water to the methacrylic acid to the octylphenol polyoxyethylene ether to the polyethyleneimine to the sodium methacrylate to the hydrophilic nano silicon dioxide is 20:3:5:3:3:100.
The modified polyester fiber is prepared by the following method: heating water to 85 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 5:100:1:100.
The alkali-free rapid hardening component comprises aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to the mass ratio of 20:2:2:3 mixing.
A preparation method of a marine concrete admixture with impermeability and corrosion resistance comprises the following steps:
A. preparing modified polyester fiber: heating water to 85 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 5:100:1:100;
B. preparing composite nano silicon dioxide: heating water to 40 ℃, dissolving sodium methacrylate in the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide;
C. 10 parts of polycarboxylate water reducer, 0.2 part of reinforcing component, 0.1 part of corrosion inhibition and rust prevention auxiliary agent, 2 parts of composite nano silicon dioxide, 10 parts of modified polyester fiber, 5 parts of alkali-free rapid hardening component, 0.1 part of air entraining agent and 25 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
Example 2
The marine concrete composite additive with impermeability and corrosion resistance is prepared from the following raw materials in parts by weight: 12 parts of polycarboxylate water reducer, 1 part of reinforcing component, 0.3 part of corrosion inhibition and rust prevention auxiliary agent, 4 parts of composite nano silicon dioxide, 12 parts of modified polyester fiber, 8 parts of alkali-free quick setting component, 0.4 part of air entraining agent and 30 parts of water.
The reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1:2 mixing.
The corrosion and rust inhibition auxiliary agent comprises the components of dodecenyl succinic acid and hydroxyethylidene diphosphonic acid according to the mass ratio of 1:2 mixing.
The preparation method of the composite nano silicon dioxide comprises the following steps: heating water to 45 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
The purity of the hydrophilic nano silicon dioxide is more than 99.8%, the average grain diameter is 7-8nm, and the specific surface area is 380+/-30 m 2 /g；
The mass ratio of the water to the methacrylic acid to the octylphenol polyoxyethylene ether to the polyethyleneimine to the sodium methacrylate to the hydrophilic nano silicon dioxide is 25:4:8:4:4:100.
The modified polyester fiber is prepared by the following method: heating water to 85 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 8:100:2:100.
The alkali-free rapid hardening component is formed by mixing aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to a mass ratio of 22:3:3:5.
A preparation method of a marine concrete admixture with impermeability and corrosion resistance comprises the following steps:
A. preparing modified polyester fiber: heating water to 85 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 8:100:2:100;
B. preparing composite nano silicon dioxide: heating water to 45 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
C. 12 parts of polycarboxylate water reducer, 1 part of reinforcing component, 0.3 part of corrosion inhibition and rust prevention auxiliary agent, 4 parts of composite nano silicon dioxide, 12 parts of modified polyester fiber, 8 parts of alkali-free rapid hardening component, 0.4 part of air entraining agent and 30 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
Example 3
The marine concrete additive for resisting salt corrosion is prepared from the following raw materials in parts by weight: 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of composite nano silicon dioxide, 15 parts of modified polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 35 parts of water.
The reinforcing component is prepared by mixing polymeric polyol and monoethanol diisopropanolamine according to a mass ratio of 1:3.
The corrosion and rust inhibition auxiliary agent comprises dodecenyl succinic acid and hydroxyethylidene diphosphonic acid which are mixed according to the mass ratio of 1:3.
The preparation method of the composite nano silicon dioxide comprises the following steps: heating water to 50 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
The purity of the hydrophilic nano silicon dioxide is more than 99.8%, the average grain diameter is 7-8nm, and the specific surface area is 380+/-30 m 2 /g；
The mass ratio of the water to the methacrylic acid to the octylphenol polyoxyethylene ether to the polyethyleneimine to the sodium methacrylate to the hydrophilic nano silicon dioxide is 30:5:10:5:5:100.
The modified polyester fiber is prepared by the following method: heating water to 90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 10:100:3:100.
The alkali-free rapid hardening component is formed by mixing aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to a mass ratio of 25:4:4:7.
A preparation method of a marine concrete composite additive with impermeability and corrosion resistance comprises the following steps:
A. preparing composite nano silicon dioxide: heating water to 50 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide;
B. preparing modified polyester fiber: heating water to 90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 10:100:3:100;
C. 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of composite nano silicon dioxide, 15 parts of modified polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 35 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
Example 4
The marine concrete composite additive with impermeability and corrosion resistance is prepared from the following raw materials in parts by weight: 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of composite nano silicon dioxide, 15 parts of modified polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water.
The reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1:3 mixing.
The corrosion and rust inhibition auxiliary agent comprises the components of dodecenyl succinic acid and hydroxyethylidene diphosphonic acid according to the mass ratio of 1:2 mixing.
The preparation method of the composite nano silicon dioxide comprises the following steps: heating water to 50 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
The purity of the hydrophilic nano silicon dioxide is more than 99.8%, the average grain diameter is 7-8nm, and the specific surface area is 380+/-30 m 2 /g；
The mass ratio of the water to the methacrylic acid to the octylphenol polyoxyethylene ether to the polyethyleneimine to the sodium methacrylate to the hydrophilic nano silicon dioxide is 30:5:5:3:5:100.
The modified polyester fiber is prepared by the following method: heating water to 90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 10:100:1:100.
The alkali-free rapid hardening component is formed by mixing aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to a mass ratio of 25:2:4:3.
A preparation method of a marine concrete composite additive with impermeability and corrosion resistance comprises the following steps:
A. preparing composite nano silicon dioxide: heating water to 50 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide;
B. preparing modified polyester fiber: heating water to 90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 10:100:1:100.
C. 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of composite nano silicon dioxide, 15 parts of modified polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
Comparative example 1
The marine concrete additive is prepared from the following raw materials in parts by weight: 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of hydrophilic nano silicon dioxide, 15 parts of modified polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water.
The reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1:3 mixing.
The corrosion and rust inhibition auxiliary agent comprises the components of dodecenyl succinic acid and hydroxyethylidene diphosphonic acid according to the mass ratio of 1:2 mixing.
The modified polyester fiber is prepared by the following method: heating water to 90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 10:100:1:100.
The alkali-free rapid hardening component is formed by mixing aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to a mass ratio of 25:2:4:3.
The preparation method of the marine concrete additive comprises the following steps:
A. preparing modified polyester fiber: heating water to 90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 10:100:1:100;
B. 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of hydrophilic nano silicon dioxide, 15 parts of modified polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain a marine concrete composite additive;
the comparative example was the same as example 4 except that the hydrophilic nanosilicon dioxide was not subjected to the complex modification, i.e., nanosilicon dioxide was directly used.
Comparative example 2
The marine concrete additive is prepared from the following raw materials in parts by weight: 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of composite nano silicon dioxide, 15 parts of polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water.
The reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1:3 mixing.
The corrosion and rust inhibition auxiliary agent comprises the components of dodecenyl succinic acid and hydroxyethylidene diphosphonic acid according to the mass ratio of 1:2 mixing.
The preparation method of the composite nano silicon dioxide comprises the following steps: heating water to 50 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
The purity of the hydrophilic nano silicon dioxide is more than 99.8%, the average grain diameter is 7-8nm, and the specific surface area is 380+/-30 m 2 /g；
The mass ratio of the water to the methacrylic acid to the octylphenol polyoxyethylene ether to the polyethyleneimine to the sodium methacrylate to the hydrophilic nano silicon dioxide is 30:5:5:3:5:100.
The alkali-free rapid hardening component is formed by mixing aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to a mass ratio of 25:2:4:3.
A marine concrete admixture comprises the following steps:
A. preparing composite permeable organic silicon: heating water to 50 ℃, dissolving sodium methacrylate into the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether (n > 7), mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, finally dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite permeable organosilicon;
B. 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of composite penetrating type organic silicon, 15 parts of polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
The comparative example was the same as example 4 except that the polyester fiber was not modified, i.e., the polyester fiber was directly used.
Comparative example 3
The marine concrete additive is prepared from the following raw materials in parts by weight: 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of hydrophilic nano silicon dioxide, 15 parts of polyester fiber, 10 parts of alkali-free quick setting component, 0.5 part of air entraining agent and 30 parts of water.
The reinforcing component is polymerized polyol and monoethanol diisopropanolamine according to the mass ratio of 1:3 mixing.
The corrosion and rust inhibition auxiliary agent comprises the components of dodecenyl succinic acid and hydroxyethylidene diphosphonic acid according to the mass ratio of 1:2 mixing.
The alkali-free rapid hardening component is formed by mixing aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to a mass ratio of 25:2:4:3.
A marine concrete admixture comprises the following steps:
A. 15 parts of polycarboxylate water reducer, 2 parts of reinforcing component, 0.5 part of corrosion inhibition and rust prevention auxiliary agent, 5 parts of hydrophilic nano silicon dioxide, 15 parts of polyester fiber, 10 parts of alkali-free rapid hardening component, 0.5 part of air entraining agent and 30 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
The comparative example was the same as example 4 except that the hydrophilic nanosilicon dioxide was not subjected to the composite modification, i.e., the hydrophilic nanosilicon dioxide and the polyester fiber were directly used.
Performance testing
The testing method comprises the following steps:
the practical application properties of the additives obtained in examples 1 to 4 and comparative examples 1 to 3 were respectively tested.
Concrete anti-Cl according to ASTM1202 - Cl in permeability electric measurement method and JTJ275-2000 corrosion protection technical Specification for seaport engineering concrete structure - The permeability rapid determination method determines the electric flux.
The concrete carbonization depth was measured according to the accelerated carbonization test in test method Standard for Long-term Properties and durability of ordinary concrete (GB/T50082-2009). The carbonization test uses a cubic concrete specimen with a side length of 100 mm.
The test method of the strength slump and other performances is referred to GB/T50080-2002 standard of ordinary concrete mixture performance test method and GB/T50081-2002 standard of ordinary concrete mechanical performance test method, and the test size is 40mm multiplied by 160mm. The concrete mix ratios of the test groups are shown in Table 1.
TABLE 1 concrete mix ratio kg/m 3
| Marine cement | Water and its preparation method | Standard sand | Marble stone | Small stone |
| 460 | 220 | 760 | 280 | 650 |
The results of the concrete performance test are shown in Table 2
TABLE 2 results of chloride Performance test
Simulation seawater dry-wet cycle test
The simulated seawater dry and wet cycle test is based on the operability of the test and the time of the seawater tide. Firstly, placing a concrete test block subjected to standard curing for 28 days at normal temperature, wherein the mass fraction of Na is 5% 2 SO 4 Soaking in 5% NaCl mixed solution for 16 hr, taking out, drying for 1 hr, oven drying at 80deg.C for 6 hr, cooling for 1 hr, one cycle for 24 hr, and then placing back into solution for soaking. The mass and the compressive strength are measured once every 25 cycles, and the mass change and the compressive strength change are compared to analyze and simulate the erosion damage condition of seawater to the test block. The experimental results are shown in table 3:
table 3 simulation results of Dry-Wet cycle experiments
From the experimental data in the table, it can be seen that the concrete test block added with the additive of the example set of the invention exhibits good erosion resistance, and the compressive strength of 50MPa is still maintained after 75 cycles of drying and wetting. In contrast, comparative example 1, in which no modification of nanosilica was performed, comparative example 2, in which no modification of fibers was performed, and comparative example 3, in which neither was performed, had a synergistic effect between the composite nanosilica and the raw materials such as the modified polyester fibers disappeared, and therefore, corrosion resistance was lowered to some extent. Therefore, the raw materials and the modification method are key to realizing good salt and corrosion resistance of the concrete, and have weak effect.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (9)
1. The marine concrete composite additive is characterized by comprising the following raw materials in parts by weight: 10-15 parts of polycarboxylate water reducer, 0.2-2 parts of reinforcing component, 0.1-0.5 part of corrosion and rust prevention auxiliary agent, 2-5 parts of composite nano silicon dioxide, 10-15 parts of modified polyester fiber, 5-10 parts of alkali-free rapid hardening component, 0.1-0.5 part of air entraining agent and 25-35 parts of water.
2. The marine concrete composite admixture for impermeability and corrosion resistance according to claim 1, wherein the reinforcing component comprises polymeric polyol and monoethanol diisopropanolamine in a mass ratio of 1: 1-3.
3. The anti-seepage and anti-corrosion marine concrete composite additive according to claim 1, wherein the corrosion and rust prevention auxiliary agent is dodecenyl succinic acid and hydroxyethylene diphosphonic acid according to the mass ratio of 1: 1-3.
4. The marine concrete composite admixture of claim 1, wherein the composite nano silica is prepared by the following steps: heating water to 40-50 ℃, dissolving sodium methacrylate in the water to keep the temperature constant, sequentially adding polyethyleneimine and octyl phenol polyoxyethylene ether, mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide.
5. The marine concrete composite admixture of claim 4, wherein said hydrophilic nanosilica has a purity of > 99.8%, an average particle diameter of 7-8nm and a specific surface area of 380+ -30 m 2 /g。
6. The anti-seepage and anti-corrosion marine concrete composite additive according to claim 4, wherein the mass ratio of the water, the methacrylic acid, the octyl phenol polyoxyethylene ether, the polyethyleneimine, the sodium methacrylate and the hydrophilic nano silica is 20-30:3-5:5-10:3-5:3-5:100.
7. The marine concrete composite admixture of claim 1, wherein the modified polyester fiber is prepared by the following steps: heating water to 85-90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 5-10:100:1-3:100.
8. The anti-seepage and anti-corrosion marine concrete composite additive according to claim 1, wherein the alkali-free rapid hardening component comprises aluminum sulfate, triethanolamine, crude mixed glycerol and magnesium aluminum silicate according to the mass ratio of 20-25:2-4:2-4: 3-7.
9. A method of preparing a marine concrete composite admixture as defined in any one of claims 1 to 8, comprising the steps of:
A. preparing composite nano silicon dioxide: heating water to 40-50 ℃, dissolving sodium methacrylate in the water to keep the temperature constant, sequentially adding polyethyleneimine and octylphenol polyoxyethylene ether, mixing and stirring uniformly for 30min, then adding hydrophilic nano silicon dioxide, stirring for 40min, dropwise adding methacrylic acid while stirring for 60min, continuously stirring for 30min after the dropwise adding is finished, and finally cooling to room temperature to obtain the composite nano silicon dioxide;
B. preparing modified polyester fiber: heating water to 85-90 ℃, adding water-soluble polyvinyl alcohol fibers into the water, stirring until the water-soluble polyvinyl alcohol fibers are completely dissolved, adding polyester fibers, stirring uniformly, slowly adding ester quaternary ammonium salt while stirring, and finally cooling and drying to obtain modified polyester fibers; the mass ratio of the water-soluble polyvinyl alcohol fiber to the polyester fiber to the ester quaternary ammonium salt to the water is 5-10:100:1-3:100;
C. 10-15 parts of polycarboxylate water reducer, 0.2-2 parts of reinforcing component, 0.1-0.5 part of corrosion and rust prevention auxiliary agent, 2-5 parts of composite nano silicon dioxide, 10-15 parts of modified polyester fiber, 5-10 parts of alkali-free quick setting component, 0.1-0.5 part of air entraining agent and 25-35 parts of water are sequentially added into water according to parts by weight, and stirred for 30 minutes to obtain the marine concrete composite additive.
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| CN107475801A (en) * | 2017-08-30 | 2017-12-15 | 广州弘雅服装科技有限公司 | Moisture absorption antistatic antibiotic polyester fiber, moisture absorption antistatic antibacterial fabric and preparation and application |
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